The present invention relates to a process for the preparation of 2,6-dimethylnaphthalene comprising reacting a naphthalene substrate with at least one aromatic hydrocarbon in the presence of a zeolitic catalyst, wherein the naphthalene substrate consists of a cut which, obtained by subjecting suitable petrochemical streams to fractionation, is treated with a bed consisting of a solid acid, before being fed to the synthesis of 2,6-dimethylnaphthalene.
2,6-dimethylnaphthalene is an intermediate for the preparation of 2,6-naphthalenedicarboxylic acid, used for obtaining PEN, polyethylenenaphthalene, a polymeric material much better than PET, polyethyleneterephthalate, for various applications.
Industrial processes for obtaining 2,6-dimethylnaphthalene are based on its recovery from fractions coming from the reforming of kerosene (JP338535xe2x80x94Nippon Mining; U.S. Pat. No. 963,248xe2x80x94Nippon Mining; JP02247136xe2x80x94Nippon Mining; JP02247137xe2x80x94Nippon Mining; JP02304034xe2x80x94Mitsubishi Oil), or from fractions of FCC oil (Chemical Week, Apr. 11, 1992, page 39; Chemical Marketing Reporter, Dec. 10, 1992; European Chemical News, Sep. 28, 1992, page 30; Chemical Week, Jun. 24, 1992, page 27). In the former case, the dimethylnaphthalenes must be separated by distillation and then the 2,6 isomer is isolated by means of selective absorptions and/or crystallizations. In the latter case, there is an additional problem due to the presence of nitrogen and sulfur which poison the catalysts used for the separation and/or isomerization phases.
There is a synthesis process (U.S. Pat. Nos. 4,990,717; 5,118,892; 5,073,670; 5,030,781; 5,012,024), which, by means of alkenylation, cyclization, dehydrogenation, isomerization steps, results in the selective synthesis of 2,6-dimethylnaphthalene, the first step starting from o-xylene and 1,3-butadiene. Alkylation on the part of butadiene on one of the methyl groups of o-xylene, takes place in the presence of a basic catalyst, with the formation of 5-(o-tolyl)2-pentene. The latter is separated and, in the presence of a zeolitic catalyst (Y-type) containing Pt and Cu, is subjected to an internal cyclization reaction. In this way 1,5-dimethyltetraline is formed, which is subsequently dehydrogenated with the help of a Pt/Re catalyst supported on alumina. This is followed by a separation phase to isolate the 1-5-dimethylnaphthalene, which is then isomerized to 2,6 with another zeolitic catalyst.
As can be seen, there are various passages in this synthesis method. This represents a problem from an economic point of view. In addition there are secondary reactions with every passage (chemical reaction) and consequently separations are necessary to guarantee the purity of the intermediates or end-product. The use of a basic catalyst containing Na and K as such or supported, in this particular process, creates handling and safety problems.
The patent U.S. Pat. No. 5,043,501 relates to a synthesis method of 2,6-dimethylnaphthalene in two steps only. The first step comprises the alkylation of an alkylaromatic with a C5 olefin in the presence of a zeolitic catalyst (MCM22). The alkylated product is then dehydrocyclized at 400-500xc2x0 C. with a catalyst consisting of Pt/Ba/K on L zeolite, obtaining a product containing dimethylnaphthalenes which are then isomerized mainly to 2,6; also in this case there are the problems mentioned above.
Another precursor of 2,6-naphthalenedicarboxylic acid (NDC) is 2,6-di-isopropylnaphthalene. The industrial preparation of this intermediate is described in patents U.S. Pat. Nos. 5,003,120; 5,003,122; 5,026,492. A disadvantage of this process is that the oxidation to carboxylic group of the isopropyl function is more expensive than that of the methyl function.
It is evident, however, that the greatest obstacle in the wide-scale use of PEN lies in the cost of the monomer, 2,6-naphthalene dicarboxylic acid (NDC) (2,6-Naphthalene Dicarboxylic Acid Precursors, May 1993, Chem Systems; High Performance Polyesters, November 1996, Chem Systems; H. P. Muhs, Polyesters Technologies for Fibres and Packaging, De Witt Petrochemical Review, 1997; J. Caldwell, PEN Outlook and Review, De Witt Petrochemical Review, 1998). It is therefore understandable how important it is, regardless of the preparation procedure followed, to be able to intervene in one or more steps of these procedures to obtain a simple and inexpensive selective synthesis of 2,6-dimethylnaphthalene.
The same Applicant, in co-pending Italian patent application MI98A000809 filed on Apr. 17, 1998, described a process for the preparation of 2,6-dimethylnaphthalene starting from naphthalene, methylnaphthalenes, dimethylnaphthalenes, trimethylnaphthalenes and/or polymethylnaphthalenes carried out under at least partially liquid phase conditions and in the presence of suitable aromatic hydrocarbons, catalyzed by a zeolite of the MTW structural type (abbreviation IZA), which allows the selective synthesis of 2,6-dimethylnaphthalene in a single step.
MTW zeolites in particular, when used under the process conditions of this patent application, are more active than the zeolites used according to the conditions described in the known art, especially with respect to BEA and MFI zeolites considered by the known art as being the best catalysts for the preparation of 2,6-dimethylnaphthalene.
The Applicant has now found, and this is an object of the present invention, that it is possible to effect these syntheses, again regardless of the particular procedure followed, using a feeding stream which can be obtained simply and at very competitive costs.
The present invention, in fact, relates to the use, in the synthesis of 2,6-dimethylnaphthalene, of a naphthalene cut obtained by the fractionation of petrochemical streams and the subsequent acid treatment of the product thus obtained.
The present invention relates in particular to a process for the preparation of 2,6-dimethylnaphthalene which comprises reacting, with at least one aromatic hydrocarbon, a mixture of naphthalenes comprising a cut obtained by the fractionation of suitable petrochemical streams and the subsequent treatment of the product thus obtained with a solid acid.
Significant and relatively xe2x80x9ccleanxe2x80x9d quantities of naphthalenes are contained in fractions such as FOK (Fuel Oil Cracking), LCO (Light Cicle Oil) and heavy fractions from catalytic reforming which are not widely exploited at the moment (for example FOK is used as fuel in certain cases). These form an economic source of naphthalenes which can be separated by distillation. For this purpose FOK or LCO petrochemical streams are subjected to fractionation to obtain the specific cut, which contains at least 20% of useful naphthalenes (mainly naphthalene and methylnaphthalenes). During this fractionation, which is carried out using conventional distillation methods, other components are inevitably separated together with the useful naphthalenes. These distill together with the useful naphthalenes because their boiling points fall within the temperature range corresponding to the separation of the cut in question.
Using this cut as naphthalene source for the synthesis of 2,6-dimethylnaphthalene, we have found that, operating according to the object of the present invention, the life of the catalyst can be considerably increased when the feeding to the synthesis of 2,6-dimethylnaphthalene is treated on a pre-bed consisting of solid acid.
The present invention therefore relates to an improved process for the preparation of 2,6-dimethylnaphthalene comprising the following steps:
fractionation of a petrochemical stream selected from FOK and LCO;
treatment of the naphthalene cut thus obtained with an acid catalyst;
sending the product thus obtained for reaction with the desired aromatic hydrocarbon in the presence of a catalyst of a zeolitic nature.
Mention has been made of the meaning of the FOK and LCO fractions. As specified, these are subjected to fractionation according to the conventional distillation methods, well known to experts in the field, which can, for example, be effected on a plate column, under vacuum.
The naphthalene cut thus obtained is subjected to treatment with a solid acid, which is effected by sending the cut, before feeding to the synthesis of 2,6-dimethylnaphthalene, onto a pre-bed consisting of said solid acid.
The treatment can take place in batch or in continuous and is carried out at a temperature ranging from room temperature to 360xc2x0 C., and at a pressure which is such as to guarantee that the operation takes place in liquid phase. The quantity of solid acid varies, with respect to the liquid to be treated, from 0.1% to 5% by weight; the WHSV(hxe2x88x921) can vary from 0.1 to 6. Solid acid materials can be used for the purpose, either totally or partially acid, such as clays (montmorillonites, smectites . . . ), or their phyllosilicatic constituents, zeolites, sulfated zirconia, acid resins (for example sulfonic resins), activated and non-activated alumina (optionally chlorinated or fluorinated), acid oxides in general, also in mixtures, amorphous silico-aluminas. Acids and heteropolyacids such as for example H3PO4 supported on kieselguhr, can also be used.
The reaction of the treated product thus obtained, with the aromatic hydrocarbon for the preparation of 2,6-dimethylnaphthalene or its derivatives, can be effected according to any of the methods known to experts in the field, or, preferably according to the particular process described and claimed in co-pending patent application MI98A 000809 filed on Apr. 17, 1998 by the same Applicant, of which the paragraphs of interest are provided hereunder and form an integrant part of the description of the invention according to the present application.
According to this application, the reaction between the naphthalene hydrocarbon (the above cut pretreated in the case of the process of the present application) and one or more benzene hydrocarbons is carried out, under at least partially liquid phase conditions, in the presence of a zeolite belonging to the MTW structural type and, optionally in the presence of a methylating agent.
Zeolites of the MTW structural type which can be used in the present invention are, for example: ZSM-12, CZH-5, Nu-13, Theta-3 and TPZ-12.
The CZH-5 zeolite is described in GB 2079735A; Nu-1 is described in EP 59059; Theta-3 is described in EP 162719 and TPZ in U.S. Pat. No. 4,557,919.
The MTW structural type zeolite, which is the most suitable for use in the present invention, is a silico-aluminate with a molar ratio SiO2/Al2O3 greater than or equal to 20.
This zeolite and its preparation are described in A. Katovic and G. Giordano, Chem. Ind. (Dekker) (Synthesis of Porous Materials) 1997 69, 127-137. The aluminum can be wholly or partly substituted by B, Ga, Fe or their mixtures as described by Toktarev and Jone, in Chon et al., Progress in Zeolites and Microporous Materials, SSSC, vol. 105, 1997.
According to a preferred aspect, ZSM-12 zeolite is used, a porous crystalline material having in its calcined and anhydrous form a molar composition of oxides corresponding to the following formula:
1.0xc2x10.4 M2/nO.W2O3.20-500 YO2.zH2O
wherein M is H+ and/or a cation of an alkaline or earth alkaline metal with a valency n, W is selected from aluminum, gallium or their mixtures, Y is selected from silicon and germanium, z ranges from 0 to 60. M is preferably selected from sodium, potassium, hydrogen or their mixtures, W is preferably aluminum and Y is preferably silicon. W can be, at least partially, substituted by boron, iron or their mixtures; the ZSM-12 zeolite is described in U.S. Pat. No. 3,832,449, in Ernst et al., Zeolites, 1987, Vol. 7, September, and in Toktarev and Ione, Chon et al., Progress in Zeolites and Microporous Materials, SSSC, vol. 105, 1997.
A particularly preferred aspect is that the MTW type zeolite used, is in the form in which the cationic sites present in its structure are at least 50% occupied by hydrogen ions. It is especially preferred for 90% of the cationic sites to be occupied by hydrogen ions.
The zeolite can be used as such, pellitized in pure form, or extruded with suitable inorganic binding oxides to form cylindrical, spherical pellets, or having other shapes commonly used, or obtained in the form of microspheres by means of spray-drying, after mixing with a ligand. The ligands may be, for example, aluminas, silicas, silico-aluminas, titania, zirconia or clays. Alumina is preferably used. In the bound catalyst, the zeolite and ligand are in a weight ratio ranging from 10:90 to 90:10, preferably from 25:75 to 75:25.
It is obviously necessary to operate in the presence of the methylating agent when only benzene is used as benzene hydrocarbon together with naphthalene alone as naphthalene substrate.
The feeding of the benzene hydrocarbon is such as to obtain a molar ratio between said hydrocarbon and the naphthalene groups ranging from 1 to 100, more preferably from 3 to 20, wherein naphthalene groups refer to the naphthalene hydrocarbon used as substrate or, when several naphthalene hydrocarbons are present, the sum of their moles.
When the process of the present invention is carried out in the presence of a non-aromatic methylating agent, preferably methanol, a molar ratio between methylating agent and naphthalene groups of less than 30, preferably from 0.1 to 3, is used.
The reaction temperature ranges from 200xc2x0 C. to 450xc2x0 C., preferably from 250 to 390xc2x0 C., even more preferably from 280 to 350xc2x0 C.; the WHSV space velocity ranges from 0.01 to 8 hoursxe2x88x921, preferably from 0.05 to 1 hourxe2x88x921.
It should be noted that the combination between the temperature and pressure conditions should be such as to guarantee that the synthesis of 2,6-dimethylnaphthalene takes place at least partially in liquid phase, and even more preferably substantially in liquid phase.
The pressure used can range from 3 to 60 atm.
The process of the present invention can be industrially carried out in continuous, semi-continuous or batchwise; in order to maintain the temperature within a preferred range, the catalyst can be distributed in various layers in the reactor. A quenching with naphthalene, with the hydrocarbon, or mixture of benzene hydrocarbons used in the process itself, or with the methylating agent, preferably methanol, when present, can be effected between one layer and another.
The temperature control can be obtained, in addition to quenching with reagents and/or inert products, also by inter-cooling between the layers, for example, by the inter-positioning of coolers. The synthesis of 2,6-dimethylnaphthalene can be suitably carried out either in a single reactor in which the catalyst is arranged in two or more beds or in two or more reactors in series, inter-cooled for the temperature control.
When an alkylating agent is used, it can be fed in two or more steps. The alkylating agent is preferably fed in two or more steps along the catalytic beds of the reactor or between these, and/or between the reactors situated in series.
According to a preferred aspect, in order to maximize the production of 2,6-dimethylnaphthalene, the product obtained according to the process of the present invention can be separated into:
(a) a fraction containing benzene hydrocarbons, naphthalene and methylnaphthalene, (b) a fraction containing dimethylnaphthalenes and (c) a fraction containing polymethylated naphthalenes. The desired 2,6-dimethylnaphthalene isomer is isolated from fraction (b) of dimethylnaphthalenes, whereas the remaining fraction (d), containing dimethylnaphthalenes different from the 2,6 isomer, and fractions (a) and (c), are re-fed to the initial reactor where they re-enter the reactive cycle. Alternatively, said fraction (d) and fractions (a) and (c), optionally enriched with naphthalene and/or methylnaphthalene, can be fed to a specific reactor where they are reacted, under at least partially liquid phase conditions, in the presence of a zeolite belonging to the MTW structural type, with one or more benzene hydrocarbons selected from benzene, toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, pentamethylbenzene and/or hexamethylbenzene. The reaction temperature ranges from 200 to 450xc2x0 C., and the space velocity ranges from 0.01 to 8 hrsxe2x88x921.
According to another aspect of the present invention, in order to maximize the production of 2,6-methylnaphthalene, fraction (d) containing dimethylnaphthalenes different from 2,6-dimethylnaphthalene, in particular 1,6 and 1,5 isomer, is subjected to isomerization, under at least partially liquid phase conditions, in the presence of a catalyst containing an MTW zeolite, at a temperature ranging from 100 to 400xc2x0 C., more preferably from 120 to 250xc2x0 C., even more preferably from 130 to 200xc2x0 C.
This particular isomerization process of 1,6-dimethylnaphthalene and 1,5-dimethylnaphthalene, pure or mixed with other isomers of dimethylnaphthalene, to give 2,6-dimethylnaphthalene, catalyzed by a zeolite of the MTW type, is in itself new and is a further object of the present invention.
The exhausted catalyst deriving from the process for preparing 2,6-dimethylnaphthalene can be regenerated by means of the known combustion methods of coke or its precursors which typically account for the deactivation of the solid acid materials which catalyze reactions in which hydrocarbons are involved. We have now unexpectedly found a method for regenerating this exhausted catalyst in a much simpler and more economic way.
With respect to the traditional regenerative methods, this new method does not require either the removal of the catalyst from the reaction environment or the high temperatures necessary for the combustion of coke. A further aspect of the present invention therefore relates to a method for regenerating the exhausted catalyst deriving from the preparation process of 2,6-dimethylnaphthalene by the reaction of a naphthalene hydrocarbon selected from naphthalene, methylnaphthalenes, dimethylnaphthalenes, trimethylnaphthalenes, tetramethylnaphthalenes, pentamethylnaphthalenes, hexamethylnaphthalene or their mixtures with one or more benzene hydrocarbons selected from benzene, toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, pentamethylbenzene and/or hexamethylbenzene, under at least partially liquid phase conditions, in the presence of a zeolite belonging to the MTW structural type and optionally in the presence of a methylating agent, wherein said regeneration method comprises treating the exhausted catalyst with one or more of said benzene hydrocarbons, at a temperature ranging from 200xc2x0 to 450xc2x0 C., more preferably from 250xc2x0 to 400xc2x0 C., even more preferably from 280xc2x0 to 370xc2x0 C., said temperature being at least equal to that used during the preparation process of 2,6-dimethylnaphthalene from which the exhausted catalyst derives. The regeneration conditions are selected so as to operate in at least partially liquid phase, the WHSV space velocity can range from 0.01 to 8 hoursxe2x88x921 and the pressure can be selected from 5 to 60 atm.
Further details can be obtained on reading the following operating examples which provide a better illustration of the invention without limiting its scope.